Let $F/K$ be a field extension, and let $\alpha \in F$. If $K(\alpha)/K$ is finite, then a $K$-isomorphism $\sigma \colon K(\alpha) \to K(\alpha)$ is uniquely determined by the image of $\alpha$ (as from that we can deduce the image of an arbitrary element by writing the latter as a polynomial expression in $\alpha$ of finite degree and using the homomorphism properties of $\sigma$).
Is there an example, when $K(\alpha)/K$ is infinite, of $K$-isomorphisms $\sigma, \sigma' \colon K(\alpha) \to K(\alpha)$ with $\sigma(\alpha) = \sigma'(\alpha)$ but $\sigma \ne \sigma'$?
The answer to the original question is no, there are no such examples.
Following Thorgott's hint, we can prove this more general statement:
Indeed, define the set: $$ A := \{x \in K' \mid \sigma(x) = \sigma'(x)\} \subseteq K' $$ Then:
$A$ is a subfield of $F$. Indeed:
By the three-step subfield test we conclude that $A$ is a subfield of $F$ (so, in particular, $A$ is a field).
$A$ contains $K$ and $\alpha_1, \ldots, \alpha_n$. Indeed, $K \subseteq A$ is due to the fact that both $\sigma$ and $\sigma'$ fix $K$ pointwise. Also, $\alpha_i \in A$ is true by hypothesis ($\sigma(\alpha_i) = \sigma'(\alpha_i)$) for all $i$.
So, by definition, this implies that $K' = K(\alpha_1, \ldots, \alpha_n) \subseteq A$. The inclusion $K' \supseteq A$ is direct from construction. Therefore $A = K'$. This means that $\sigma$ and $\sigma'$ agree on their entire domain, so $\sigma = \sigma'$.